Spectrally sensitized silver halide photographic emulsion

ABSTRACT

A silver halide emulsion spectrally sensitized with a combination of a cyanine dye of the general formula (I) as hereinafter defined and a cyanine dye of the general formula (II) as hereinafter defined and having spectral sensitivity in the wave length region ranging from 580 nm to 640 nm.

nited States Patent Hinata et al.

[ Mar. 25, 1975 SPECTRALLY SENSITIZED SILVER HALIDE PHOTOGRAPHICEMULSION Inventors: Masanao Hinata; Haruo Takei;

Keisuke Shiba, all of Kanagawa, Japan Assignee: Fuji Photo Film Co.,Ltd.,

Kanagawa, Japan Filed: Feb. 28, 1974 Appl. No.: 447,114

Foreign Application Priority Data Feb. 28, 1973 Japan 48-23987 U.S. Cl.96/124, 96/100 Int. Cl G03c 1/14 Field of Search 96/124, 137, 100

[56] References Cited UNITED STATES PATENTS 3,666,480 5/1972 Shiba eta1. 96/124 3,672,898 6/1972 Schwan et a1 96/124 3,702,251 11/1972 Satoet al 6/124 3,799,783 3/1974 Hill et al. 96/124 Primary Examiner-J.Travis Brown Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn &Macpeak 13 Claims, 18 Drawing Figures SPECTRALLY SENSITIZED SILVERHALIDE A further object of the present invention is to selec-PHOTOGRAPHIC EMULSION tively find supersensitizing dyes which, whenincorporated in one layer of a multi-layered light sensitive ma-BACKGROUND OF THE INVENTION terial to spectrally sensitize the layerselectively so as 1. Field of the lnvention 5 to attain theabovedescribed objects of the present in- The present invention relatesto asilver halide photovention, do not diffuse into adjacent layers tocause graphic emulsion which is spectrally sensitized in aspesensitization therein. cific wave-length region by supersensitizationand, A still further object of the present invention is to moreparticularly, it is concerned with a silver halide find sensitizing dyeswhich are more selective, which photographic emulsion spectrallysensitized in a wavecause less color stain after development-processingand length region of from 580 nm to 640 nm. which cause less reductionin sensitivity even upon 2. Description of the Prior Art storage afterproduction of the light sensitive material Commonly used photographiclight-sensitive materi- (spectrally sensitized by the dyes).

als are provided with a suitable spectral sensitization distributionranging over the visible wave-length region SUMMARY OF THE INVENTION towhich the human eye is sensitive. In order to impart The above-describedobjects can be attained as folmore Suitable Color reproducibility, moreappropriate lows, i.e., by incorporating a supersensitizingcombinasensitization distribution is required. Therefore, comi n of atleast one carbocyanine dye represented by binations showingsupersensitization comprising two th f ll wi neral formula (I);

or more sensitizing dyes are being studied and selected wherein 2,represents the atoms necessary to form a for use. benzothiazole ring, abenzoselenazole ring, a B-naph- From the standpoint of obtainingexcellent color rethothiazole ring or a ,B-naphthoselenazole ring; Zrepproducibility, it is not preferable to impart high sensiresents theatoms necessary to form a benzoselenazole tivity too far in the longerwave length region, e.g., ring; A represents a hydrogen atom or an alkylgroup; longer than 660 nm (wave length of the sensitization R1 and R2each represent an alkyl group or a substimaximum) or, conversely, toimpart sensitivity only in tuted alkyl group, at least O Of 1 and 2being a a too short wave length region, e.g., less than 580 nmdroxyalkyl group, a carboxy-substituted alkyl group or (wave length ofthe sensitization maximum). a sulfo-substituted alkyl group; X,represents an acid However, in the conventional spectrally sensitizinganion group; and m represents 1 or 2 and, when the dye art. it has beendifficult to selectively increase the sensif rms an in rnal alt t in-lik Structure), H1 ptivity in the wave length region ranging from 580nm to resents l; a d at least One carbocyanine dye repre- 640 nm and thesolution of this problem has been an Se ed y the general formulaimportant subject in this art.

It is, therefore, an object of the present invention to wherein Z and Z,each represent the atoms necessary provide a novel supersensitizingcombination to selecto form a halogen-substituted benzimizadole nucleus;tively increase the sensitivity in the wave length region R, and R, eachrepresents an alkyl group or a substiranging from 580 nm to 640 nm.tuted alkyl group, at least one of R and R being a hy- Another object ofthe present invention is to provide droxyalkyl group, acarboxy-substituted alkyl group or a supersensitizing combination whichmitigates the rea sulfo-substituted alkyl group; X, represents an acidduction in sensitivity experienced in conventional comanion; and nrepresents 1 or 2 and, when the dye forms binations of supersensitizingdyes. an internal salt, n represents 1.

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 17 are spectrograms ofphotographic materials as described in the Examples and FIG. 18 showstheper cent transmission curve of the filters used in the Examples.

DETAILED DESCRIPTION OF THE INVENTION Suitable examples of substituentswhich can be present on the Z, or Z containing heterocyclic nucleus area halogen atom (e.g., chlorine, fluorine, bromine), a lower alkyl grouppreferably having no more than 4 carbon atoms in the carbon chain (e.g.,methyl, ethyl, etc.), an alkoxy group (e.g., methoxy, ethoxy, etc.), analkoxycarbonyl group (eg, methoxycarbonyl, etc.), a trifluoromethylgroup, a hydroxy group and a carboxy group.

In the general formulae (I) and (II) which represent the sensitizingdyes to be used in the present invention, the heterocyclic ring formedby Z includes, e.g., benzothiazole, 5-chlorobenzothiazole, 5-bromobenzothiazole, S-fluorobenzothiazole 5 methylbenzothiazole,5-methoxybenzothiazole, 5-

e.g., l-methyl-5-chlorobenzimidazole, l-methyl-5- fluorobenzimidazole,l-methyl-5,6- dichlorobenzimidazole, I-ethyl-S- chlorobenzimidazole,I-ethyl-5-fluorobenzimidazole, l-methyl-S ,o-dichlorobenzimidazole,l-ethyl5 ,6- difluorobenzimidazole. l-propyl-5- chlorobenzimidazole,l-propyl-5-fluorobenzimidazole, l-propyl-S ,o-dichlorobenzimidazole, lpropyl-5 ,6- difluorobenzimidazole, l-allyl-S-chlorobenzimidazole,

l-allyl5-fluorobenzimidazole, I-allyl-5,6- dichlorobenzimidazole,l-allyl-5,6- difluorobenzimidazole, l-phenyl-S- chlorobenzimidazole,l-phenyl-5-fluoroben2imidazole, I-phenyl-5,o-dichlorobenzimidazolel-phenyl-5,6- difluorobenzimidazole ring, l-acetoxyalkyl (e.g., propyl,etc.)-5,6-dichlorobenzimidazole, l-hydroxyalkyl (e.g., ethyl,etc.)-5,6-dichlorobenzimidazole, and the like.

A represents, for example, a hydrogen atom, an alkyl group, preferablyhaving up to 3 carbon atoms, e.g., a methyl group, and ethyl group, apropyl group, or the like.

R R R and R each represents an alkyl group such as an unsubstitutedalkyl group (e.g., a methyl group, an ethyl group, a propyl group), ahydroxyalkyl group (e.g., a Z-hydroxyethyl group, a 3-hydroxypropylgroup, etc.), a carboxy-substituted alkyl group (e.g., a Z-carboxyethylgroup, a 3-carboxypropyl group, a 4- carboxybutyl group. etc.), asulfo-substituted alkyl group (e.g., a 2-sulfoethyl group, a3-sulfopropyl group. a 3-sulfobutvl group. a 2I3-sulfopropoxvlethvlgroup, a 2-hydroxy-3-sulfopropyl group, a 3-sulfopropoxyethoxyethylgroup, etc.), an acetoxyalkyl group (e.g., acetoxyethyl, etc.), acyanoalkyl group (e.g., cyanopropyl, etc.), a carbamoylalkyl group(e.g., B-carbomoylethyl, etc.), a morpholinocarbanylalkyl group [e.g.,B-(4-morpholinocarbonyl)ethyl, etc.], an allyl group, a morpholinosulfonylalkyl group [e.g., 8-(4-morpholinosulfonyl)butyl, etc.], or thelike in which the alkyl moiety has, preferably up to 8 carbon atoms.

X," and X each represents an acid anion commonly employed in cyanine dyesalts, such as an iodide ion, a bromide ion, a chloride ion, ap-toluenesulfonate ion, a benzenesulfonate ion, an ethylsulfate ion, aperchlorate ion, a rhodanide ion, or the like. It is preferred that whentwo benzimidazole nuclei in the dye of general formula (II) are eachsubstituted with chlorine atom(s), one of R and R is a hydroxyalkylgroup, a carboxysubstituted alkyl group or a sulfo-substituted alkylgroup and the other is a carbamoylalkyl group, an acetoxyalkyl group, amorpholinocarbonyl group. a cyanoalkyl group, a morpholinosulfonylgroup. or an allyl group; or at least one of the nitrogen atoms at the1- position ofthe dye of general formula (II) is substituted with anaryl group. an acetoxyalkyl group or an allyl group. Incidentally.

If: R: or RI. illustrates the above.

A chemical structural feature of the sensitizing dyes represented by thegeneral formula (I) is that they are carbocyanine dyes wherein one or,preferably, two of the substitutents connected to the nitrogen atom oratoms in the nitrogen-containing heterocyclic nueleus or nuclei arehydroxyalkyl groups, carboxysubstituted alkyl groups orsulfo-substituted alkyl groups. These dyes show maximum sensitivity inthe wave length region ranging from about 600 nm to about 670 nm.Furthermore, they have the feature that, when used in combination withthe dye represented by the general formula (II), they increase thespectral sensitivity while maintaining the light sensitivity maximum ata wave length of from about 600 nm to about 630 nm.

A chemical structural feature of the sensitizing dyes represented by thegeneral formula (II) is that they are imidazolocarbocyanines having ahydroxyalkyl group, a carboxy-substitutcd alkyl group or asuIfo-substituted alkyl group as the substituent connected to thenitrogen atom in the nitrogencontaining heterocyclic nucleus. These dyesshow maximum sensitivity in the wave length region ranging from about570 to about 585 nm and scarcely cause color stain after developmentprocessing.

The supersensitizing action by the combined use of the dyes of thepresent invention strongly counteracts prevention of spectralsensitization due to presence of a color coupler. For example, thedesensitization, conventionally experienced in the combined use of asensitizing dye and a coupler, is extremely small. In addition, sincethese dyes rarely diffuse into adjacent emulsion layers when applied toone light sensitive layer of a multi-layer light sensitive material.they never sensitize the adjacent layers (silver halide emulsionlayers). The above-described effects are never adversely affected evenwhen a color sensitizer (e.g., 2,2-cyanine, thia-2- cyanine, etc.) toincrease the green-sensitivity or other color sensitizers (e.g.,thiacarbocyanine, etc.) are used in combination.

The supersensitizing technique in accordance with the present inventionare useful for the production of ortho-pan type light sensitiveemulsions, light sensitive emulsions for mult-layer coupler in theemulsion type color films, particularly, reversal color films andnegative color films, for example, as disclosed in US. Pat. Nos.2,698.794; 2,474.293; 2,600,788; 3,311,476; 3.458.315; 3,214,437 and3,253,924.

Specific examples of the sensitizing dyes which can be used in thepresent invention are illustrated below. However, the present inventionis not limited to the dyes specifically described below.

Specific examples ofthe dyes represented by the general formula (l):

Se\c (HHS /Se CH C CH C 5 (I +1) N N (lm hon Br" (Hz)zOH Se\ CH3 /Se(CHm BH H0380;

S\ /Se /C=CH-C=CHC\ J@ l l (CH; s'o n (on: ,so,

/ Se\ I /Se 1 c cu c on c cn,o lil 1 4o (CHz)zCOOH tcnzizc Specificexamples of the dyes represented by the general formula (II):

CzHs C2H5 N on c on on CH 11 I \\N at (CHz 2 )2( 2)a s- 13 14Sensitizing dyes used for comparison in demonstrating lae (I) and (II)of the present invention are described the effects of the presentinvention are as follows: below:

Se\ /Se c on c cn' 0V on: N 1;! on,

I 6 H; BI (3H5 Se f ,Se -C=CH-C=CH-C N I l I CgHs I 2 5 1 2 s $2 5 C9. nI 11 C2.

C=CH-CH=CH-C CR. N N or. I I C2H5 5t CZHS Suitable sensitizing dyeswhich can be used together mbiaatiqwitha ensr rfoml Q (Dfj CH N I N I I(CHZ)SSOS ),S0 HN(CzHs)s I CH N I I (OH: ,so, 0211;

03H; S I C 1 CH C 8 CH C N N The silver halide photographic emulsionswhich can be used in the present invention are those produced in aconventional manner and containing silver chloride, silver bromide,silver iodide, silver chlorobromide, silver chloroiodide, silverbromoiodide, silver chlorobromoiodide or mixed silver halide grainsthereof, which are precipitated through a single jet method, a doublejet method, or a combination of these methods followed by ripening. Apreferred silver halide is silver bromoiodide or silverchlorobromoiodide and a preferred mean diameter of the grains (measuredby, e.g., a projected area method or a number average method) is from0.04 micron to 2 microns. Suitable examples of and the preparationthereof are disclosed in U.S. Pat. Nos. 3,217,157; 2,222,264; 3,320,069;2,592,250; 3,206,313; and 3,367,778 and Belgian Pat. No. 704,255; U.S.Pat. NO. 2,996,382 and Klein and Moisar Journal of Photographic Science,volume 12, page 242 et seq., or Markvcki The Spectral Sensitization ofSilver Bromide Emulsion on Different Crystallographic Faces", Journal ofPhotographic Science, volume 13, 1965.

To the silver halide photographic emulsion used in the inventionconventionally employed chemical sensitization techniques such as goldsensitization (as described in U.S. Pat. Nos. 2,540,085; 2,597,856;2,597,915; 2,399,083; etc.), sensitization with a Group V111 metal ion,sulfur sensitization (as described in U.S. Pat. Nos. 1,574,944;2,278,947; 2,330,206; 2,410,689;

3,189,458; 3,415,649; etc.), reduction sensitization (as described inU.S. Pat. Nos. 2,518,698; 2,419,974; 2,983,610; etc.), or a combinationof these sensitization techniques can be employed.

More specifically, the emulsion can contain a sulfur sensitizer such asallylthiocarbamide, thiourea, sodium thiosulfate or cystine; a noblemetal sensitizer such as potassium chloroaurate, aurous thiosulfate, orpotassium chloropalladate; a reduction sensitizer such as tin chloride,phenylhydrazine or reductone; and the like. Also, the emulsion cancontain such a sensitizer as a polyoxyethylene derivative, apolyoxypropylene derivative, a quaternary ammonium group-containingderivative or the like. Furthermore, the emulsion can contain anantifogging agent such as nitrobenzimidazole or ammoniumchloroplatinate, and a stabilizing agent such as4-hydroxy-6-methyl-l,3,3a,7-tetrazaindene.

In addition, the emulsion can contain a hardener, such as formaldehyde,chrome alum, l-hydroxy-3,5- dichlorotriazine sodium salt, glyoxal,dichloroacrolein, etc., and a coating aid such as saponin, sodiumalkylbenzenesulfonate, etc.

Particularly preferred examples of hardeners are aldehyde seriescompounds such as formaldehyde, glutaraldehyde and halocarboxyaldehydes(e.g., mucochloric acid); ketones such as diacetyl andcyclopentanedione; active halogen-containing compounds such asbis(2-ch1oethyl urea), 2-hydroxy-4,6-dichloro-l ,3,5- triazine and thosecompounds as disclosed in U.S. Pat.

974,723 and 1,167,207; active olefin-containing compounds such asdivinylsulfone, 5-acetyl-l,3- diacryloylhexahydro-l,3,5-triazine andthose compounds as disclosed in U.S. Pat. Nos. 3,635,718; 2,232,763;3,490,911 and 3,642,486 and British Pat. No. 994,869; N-methylolcompounds such N-hydroxymethylphthalimide and those compounds asdisclosed in Us Pat. Nos. 2,732,316 and 2,586,168; isocyanates asdisclosed in U.S. Pat. Nos. 3,103,437; aziridines as disclosed in U.S.Pat. Nos. 3,017,280 and 2,983,611; acid derivatives as disclosed in U.S.Pat. Nos. 2,725,294 and 2,725,295; carbodiimide series compounds asdisclosed in U.S. Pat. No. 3,100,704; epoxy compounds as disclosed inU.S. Pat. No. 3,091,537; isooxazoleseries compounds as disclosed in U.S.Pat. Nos. 3,321,313 and 3,543,292; dioxane derivatives such asdihydroxydioxane and dichlorodioxane and inorganic hardeners such aschrom alum and zirconium sulfate, precursors of the above-describedmaterials such as addition compounds of an alkali metal bisulfite and analdehyde, methylol derivatives of hydrazine, and primary aliphatic nitroalcohols and those compounds as disclosed in U.S. Pat. Nos. 3,288,775;3,017,280 and 2,983,611 and British Pat. No. 1,167,207. Any of the knownsurface active agents as a coating aid can be employed and sepcifically,anionic surface active agents containing acidic groups such as acarboxylic acid group, a sulfonic acid group, a phosphoric acid group, asulfate group, a phosphate group, etc., ampholytic surface active agentsof carboxylic acid type, sulfonic acid type, sulfate type or phosphatetype; nonionic surface active agents of the polyalkyleneoxide series orthe polyglycerin series; and natural surface active agents such assaponin, are preferably used. Suitable such materials and the amountsthereof generally suitable for use are disclosed for example, in

U.S. Pat. Nos. 2,600,831; 3,068,101; 3,415,649; 3,617,286; 2,271,623;2,240,472; 2,288,226; 2,739,891; 3,158,484; 3,201,253; 3,210,191;3,294,540; 3,415,649; 3,441,413; 3,442,654; 3,475,174; 3,545,974; GermanOLS No. 1,942,665;

and British Pat. Nos. 1,077,317 and 1,198,450.

When used in a color photographic light sensitive material, the silverhalide emulsion used in the present invention contains a color couplerand a dispersing agent therefor.

Of the color couplers, a cyan coupler is particularly preferred. Forexample, the phenolic couplers as described in U.S. Pat. No. 2,698,794and the naphtholic couplers as describedin U.S. Pat. No. 2,474,293 areparticularly useful. Also, the couplers described in US. Pat. No.2,600,788, British Pat. No. 904,852 and Japanese Patent PublicationNumber 603 1/65, the a-naphtholic cyan couplers and the phenolic cyancouplers described in, e.g., U.S. Pat. Nos. 3,311,476; 3,458,315;3,214,437 and 3,253,924 can be used. For example, the couplersrepresented by the following structural formulae can be used, all ofwhich are known com- Nos. 3,288,775 and 2,732,303 and British Pat. Nos.pounds.

HzC-fi NHCO Ha 1C: 5 CONH COOH COCHzCONH COOH OCH:

- CO(|ZH CONH NHCOfHCSH? C2 O COCHzCONH NHCOCHzO C5H11('G) OCHa cslhflt)Photographic emulsions spectrally sensitized with the dye combinationsof the present invention can contain various colloids alone or incombination as vehicles or binding agents. Suitable hydrophilicmaterials include both naturally-occurring substances such as proteins,for example, gelatin, gelatin derivvtives suchas phthaloylated gelatinor malonoylated gelatin, cellulose derivatives such as hydroxyethylcellulose or carboxy methyl cellulose, polysaccharides such as dextran,gum arabic and the like; and synthetic polymeric substances such aswater soluble polyvinyl compounds, c.g., polyvinyl alcohol,poly(vinylpyrrolidone), acrylamide polymers, polystyrenesulfonic acid,or other synthetic polymeric compounds such as dispersed vinyl compoundsin latex form, and particularly those which increase the dimensionalstability of the photographic materials. Suitable synthetic polymersinclude those described, for example, in US. Pat. Nos. 3,142,568;3,193,386; 3,062,674; 3,220,844; 3,287,289 and 3,411,911. Particularlyeffective are those water insoluble polymers of alkyl acrylates andmethacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates,those which have cross linking sites which facilitate hardening orcuring and those having recurring sulfobetaine units as described inCanadian Pat. No. 774,054. As the matting agent which can also bepresent in the emulsion, there are preferably used silver halide grainsof a suitable grain size; inorganic compounds such as silica, strontiumbarium sulfate, etc.; water-dispersable vinyl polymers such aspolymethyl methacrylate, etc. Examples of plasticizers which can bepresent in the emulsion are waxes such as liquid paraffin, higher fattyacid esters, etc.; polyfluorinated hydrocarbons or derivatives thereof;

silicones such as polyalkylpolysiloxane, polyarylpolysiloxane,polyalkylarylpolysiloxane or the alkylene oxide adduct derivativesthereof; and the like are preferably used. I r

The finished emulsion is applied to a suitable support such as barytapaper, a resin-coated paper, a synthetic paper, a triacetate film, apolyethylene terephthalate film, a gl'ass plate or other plastic bases.

These addenda described above are used in an amount to achieve theirknown function and such can easily be determined by one skilled in theart.

The sensitizing dyes of the general formula (1) and (11) used in thepresent invention are added as a solution prepared by dissolving thedyes in water or a water-miscible organic solvent such as methanol,ethanol, t yl. qsq vst2y isli OI sl e- Each of these dyes is used in theamount usually employed in supersensitization, c.g., 5 X 10 mol to l X10 mol, preferably 1 X 10" mol to 1 X 10' mol, per 1 mol of silver. Apreferred molar ratio of the amount of the dye represented by thegeneral formula (11) to that of the dye represented by the generalformula (1) ranges from 1:10 to 10:], particularly 1:5 to 5:1 and moreparticularly 1:3 to 3:].

Also, the dyes to be used in the present invention can be used forspectral sensitization according to German OLS Pat No. 2,104,284 and US.Pat. No. 3,649,286.

The present invention will now be illustrated in greater detail byreference to the following examples which, however, are not intended tolimit the present invention in any way. Unless otherwise indicated. allparts, percents, ratios and the like are by weight.

23 EXAMPLE 1 ameter of 0.42 p. and this emulsion contained 0.52 molsilver halide per 1 kg. 1 kg portions of this emulsion were weighed outin a pot, which was then placed in a 50C thermostatic bath to melt theemulsion. Methanol solutions of the sensitizing dyes of the presentinvention and sensitizing dyes for comparison were added to the emulsionportions in predetermined amounts (as shown in Table I), and mixed andstirred at 40C.

To each emulsion portion were added 10 cc of a 0.1 by weight aqueoussolution of 4-hydroxy-6-methyl- I,3,3a,7-tetrazaindene, 10 cc of a 1 byweight aqueous solution of I-hydroxy-3,5-dichlorotriazole sodium saltand 10 cc of a I by weight aqueous solution of soidumdodecylbenzenesulfonate, and stirred. Each of the thus finished emulsionportions was applied to a cellulose triacetate film base in a drythickness of 5 p. and then dried. Thus, light sensitive material sampleswere obtained. Each of these film samples was cut into. strips. Three ofthe strips were wedgewise exposed using a sensitometer containing alight source of a color temperature of 5400K light source being covered,respectively, by a blue filter (Sp-I a yellow filter. (Sc- 50) and a redfilter (Sc-56) (made by the Fuji Photo 30 Film Co., Ltd.) On the otherhand, one remaining strip was exposed using a grating spectrophotographhaving a 2660K tungsten light source to obtain spectrograms.

20 Water to make The thus exposed strips were development-processed at20C for 2 minutes using a developer (D-I9) having the followingcomposition followed by stopping, fixing and washing. Thus, stripshaving given black-and-white images were obtained. The density of theseimages was measured using a S-type densitometer (made by Fuji Photo FilmCo., Ltd.). Thus, the blue filter sensitivity (S yellow filtersensitivity (5,), red filter sensitivity (S and fog were obtained. Thestandard point of the optical density to determine the sensitivity wasfog Composition of the Developer (D-I9):

Water Metol 2 Sodium Sulfite (anhydrous) 90 Hydroquinone 8 SodiumCarbonate (monohydrate) 2. Potassium Bromide 5 The results obtained areshown in Table I as the relative values.

Run Nos. 3, 4, 9 and 12 were conducted for comparison.

The spectral transmission curves of filter Sp-I, filter Sc-SO and filter80-56 are shown in FIG. 18. The spectrograms obtained are shown in FIGS.1 to 10. From the values given in Table I and from the spectrograms. itcan be seen thatthe effects of the combination of dyes of the presentinvention showing a supersensitizing action are excellent.

TABLE I Dye and Amount D e and Amount Dye and Amount No. Uscd X 10 me!sad X 10 mol Used X 10'' mol Sy* S,,* S,,* Fog spectrogram I (I A) I 16088 94 0.07 FIG. 1 1

2 280 I64 86 0.07 4 360 230 80 0.07 (11 B) I 127 75 94 0.07 2 I80 I00 860.09 4 I98 107 75 0.10 FIG. I 2 (l-A) I (II-B) 4 420 270 88 010 FIG. 1-32 4 420 285 80 0.10 2 (6) I 75 98 0.07

2 I14 100 90 0.08 FIG. 2 4 (I -A) I (II-B) 4 (6) 2 570 370 92 0.10 FIG.2-5 3 (I) I I24 53 86 0.07

2 I 73 78 0.07 FIG. 3 6 4 200 86 70 0.07 (I) I (II B) 4 328 I96 78 0.09

2 4 338 206 73 0.10 FIG. 3 7 4 (3 I 56 25 80 0.07 2 I10 46 0.09 4 I17 4968 0.11 FIG.4-8 (I-A) l (3) v4 280 I60 7 0.10

2 j 4 280 I69 67 0.10 FIG. 4 9 5 (I E) I 100 I00 88 0.07 FIG. 5 10 2 I68146 70 0.07 4 250 230 60 0.07 (I-E) I (II-B) 4 400 250 92 0.10 FIG.5-I1

2 4 420 272 84 0.10 6 (I-E) 1 (11 B) 4 (6) 2 505 358 92 0.10 7 (7) 0.5100 0.07 FIG. 6 12 1 118 96 0.07 (1-E) I (II-B) 4 (7) 0.5 480 330 960.10 FIG.6- I3 8 (4) 4 I8 100 0.07 FIG. 7 I4 8 20 92 0.08 (I-E) I (II-B)4 (4) 4 472 250 92 0.10 FIG.7-15 9 (2) I 22 I2 62 0.07

2 24 23 50 0.10 FIG. 8 l6 4 27 25 45 0.13 (2) I (II B) 4 I46 88 55 0.09

2 4 146 91 46 0.10 FIG.8-17

tion was added to a mixture, prepared by adding as an aqueous solution2.5 g of dodecylbenzenesulfonic acid to 1 kg of a 10 by weight gelatin,stirred at a high speed and subjected to ultrasonic wave stirring toemulsify. Thus, an emulsion was obtained.

1 kg portions of the silver bromoiodide emulsion prepared according tothe method of Example 1 were weighed out in a pot. which was then placedin a 50C thermostatic bath to melt the emulsions. Methanol so-' lutionsof the sensitizing dyes of the present invention and the sensitizingdyes for comparison were added to the emulsion portions in predeterminedamounts (as shown in Table 2), mixed and stirred at 40C, and then leftfor IS minutes. To each emulsion portion were added 250 g of theabove-described emulsion, l cc of a 0.1 by weight aqueous solution of4-hydroxy-6- methyl-l,3,3a,7-tetrazaindene, 10 cc of a l by weightaqueous solution of l-hydroxy-3,5- dichlorotriazine sodium salt and 10cc of a 1 by fonate, and stirred.

Each of the thus finished emulsion portions was applied to a cellulosetriacetate film base in a dry thickness of p. followed by drying. Thus,light sensitive material samples were obtained.

Each of these film samples was cut into strips. One of the strips waswedgewise exposed through a red filter Sc-56 using a sensitometercontaining a light source of a color temperature of 5400K.

This was development-processed at 24C for minutes in a developer havingthe following composition followed by washing. hardening, washing andsecond reversal exposure.

'45 weight aqueous solution of sodium dodecylbenzenesul- TABLEl-Continued Dye and Amount Dye and Amount Dye and Amount No Used X l0mol Used X 10" mol Used X 10" mol S\-* S,,* S,,* Fog spectrogram l mo 9292 0.07 FIG. 9 l8 2 I42 I30 0.08 10 (ll E) l 140 86 98 0.07 2 198 I 1090 0.08 4 230 88 008 FIG. 9 19 (l F) 0.5 (ll E) 4 395 350 92 0.08

1 4 405 358 92 0.08 FIG. 9 20 11 (I A) I (ll E1 4 432 280 96 0.08 FIG.l0 21 2 4 128 80 40 0.10 FIG. 10 22 100 0.07

* Relative value EXAMPLE 2 Composition of the Developer:

N-Methyl-p-aminophenol 4.5 g 20 Hydroquinone 4.5 g 80 grams of a cyamnecoupler, l-hydroxy-4- Sodium Sultite (anhydrous) 50 gmaleimidO-Z-naphthamide, was completely dissolved in gg tgg g gg if g amixed solution of [00 cc of tricresyl phosphate and PotassiumThiocyanate 2 g 50 cc of ethyl acetate. Furthermore, 2 g of sorbitanWate'm make I I monolaurate was dissolved therein. The resulting solu-25 The strip was then color development-processed at 24C for 15 minutesin a color developer having the following composition followed bywashing, bleaching, washing, fixing and washing. Thus, a color positiveimage was obtained.

Composition of Color Developer:

p-Amino-Nethyl-N-/3-mcthanesullonamidoethyl-m-toluidine Sulfate Water tomake the total l l The density of the thus obtained strips was measuredusing an S-type densitometer (made by Fuji Photo Film Co. Ltd.) toobtain the relative sensitivity and cyan color fog. The standard pointof the optical density to determine the sensitivity was fog 0.5. Theresults obtained are shown in Table 2.-

Run Nos. 3, 4, 7 and 8 were conducted for comparison.

On the other hand, the one remaining strip was exposed using a gratingspectrophotograph having a 2660K tungsten light source to obtainspcctrograms. The thus obtained spectrograms are shown in FIGS. 11 to17.

From the values given in Table 2 and from the spectrograms obtained, itcan be seen that the effects of the combination of dyes of the presentinvention having supersensitizing action are excellent and are affectedby the coupler with difficulty as compared with the comparative dyes.

TABLE 2 Relativc Dvc and Amount Dye and Amount D c and Amount Scnsi- Can Nu. Used X I mol Used X mol sud X I0 mol tivity F og spectrogram l (lA) 0.07

I 98 0.07 FIG. ll 23 2 I80 007 (II B) l 70 0.07 2 95 0.07 4 I03 0.08FIG. ll 24 (I-A) I (II-B) 4 I86 0.08 FIG. ll -25 2 92 007 FIG. 12 26(I-A) l (II-B) 4 (6) 2 268 0.08 FIG. 12 27 3 I) I 33 0.07

2 45 007 FIG. I3 4 28 4 52 0.07 (I) l (ll-B) 4 I55 0.08

2 4 I60 0.08 FIG. I3 29 4 (3) I 38 0.07 2 80 0.08 4 85 (H0 FIG. l4 30(I-A) l (3) 4 I50 0.]0

2 4 I50 0.l0 FIG. l4-3l 5 (l-E) I I00 007 FIG. 15-32 2 I40 0.07 (I-E) I(II-B) 4 I80 0.08 FlG.l5-33 2 4 200 0.08 6 (l-E) l (II-B) 4 (6) 2 2500.08 7 (2) I 2 0.07

2 3 0.07 FIG. I6 34 4 5 0.07 (2) I (II-B) 4 ll4 0.08

2 4 I25 0.08 FIG. I6 35 8 (3) I (3) 4 80 0.09

2 4 70 0.09 FIG. l7 36 The combination of sensitizing dyes of thepresent invention having sensitizing action is useful for spectrallysensitizing a silver halide emulsion using for a red-sensitive layer incolor light sensitive materials such as a color negative light sensitivematerial and a color reversal light sensitive material; a silver halideemulsion for use in a plate-making light sensitive material; and asilver halide emulsion for use in a light sensitive material formicrosecond exposure, particularly, a CRT sensitive material, a lightsensitive material for holography and a light sensitive material for usein a facsimile system.

In the case of using as a color light sensitive material, it ispreferable to provide a magenta or red outer filter above or adjacent tothe red-sensitive silver halide emulsion layer obtained by the presentinvention so as to impart the effect of actually reducing thegreensensitivity in contrast to the red-sensitivity. In order to formsuch filter layer. the dyes described in Japanese Pat. Nos. 18459/66,350/68, l3l68/68, 22069/64. 98474/7], 42668/71. 42667/71, US. Pat. Nos.3,440,05]; 3,468,883; 3,294,539; 3,379,533; 3,352,680; 3,389,994;3,384,487; 3,423,207; 3,493,375; 3,486,897; 3,481,927; 3,497,502;

3,573,289; 3,560,214; 3,615,432; 3,282,699; British Pat. No. 506,385,etc. can be used. In particular, those dyes which selectively absorblight of wave lengths shorter than 570 mm are useful. In addition, themethods described in German OLS No. 2,008,882, US. Pat. Nos. 3,425,834;3,282,699, Belgian Pat. Nos. 682,413; 685,292; 703,939; 627,308,Japanese Pat. Nos. 21766/68, 13498/68, 15896/70, 10254/68, etc. can beemployed. These are also employable for preventing iradiation ofhalation,

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:

1. A silver halide photographic emulsion containing a supersensitizingcombination of at least one sensitizing dye represented by the followinggeneral formula wherein Z, represents the atoms necessary to form abenzothiazole ring, a benzoselenazole ring, a B-naphthothiazole ring ora ,B-naphthoselenazole ring; Z represents the atoms necessary to form abenzoselenazole ring; A represents a hydrogen atom or an alkyl group; Rand R each represents an alkyl group, at least one of R and R being ahydroxyalkyl group, a carboxysubstituted alkyl group or asulfo-substituted alkyl group; X, represents an acid anion group; and mrepresents l or 2 and, when the dye forms an intramolecular salt, Inrepresents 1; and at least one sensitizing dye represented by thegeneral formula (II) R and R, each represents an alkyl group, at leastone of R and R, being a hydroxyalkyl group, a carboxysubstituted alkylgroup or a sulfosubstituted alkyl group; X: represents an acid anion:and n represents 1 or 2 and, when the dye forms an intramolecular salt.n represents l.

2. The silver halide photographic emulsion as described in claim 1,wherein in the general formula (I) Z, forms a ,B-naphthothiazole ring, aB-naphthoselenazole ring or a benzothiazole or benzoselenazole ringwhich is unsubstituted or substituted with a methyl group, an ethylgroup, a methoxy group, a phenyl group 30 l -allyl--fluorobenzimidazole. l -allyl 5 .odichlorobenzimidazole.l-allyl-5.odifluorobenzimidazole, l-phcnyl-5lchlorobenzimidazole.l-phenyl-S-fluorobenzimitlazolc. l-phenyI-5.6-dichlorobenzimidazole. lphcnyl-5 ,(1- difluorobenzimidazole ring; wherein said alkyl group for Ais a methyl group, an ethyl group. or a propyl group; wherein said R, toR, each is a methyl group. an ethyl group. a-propyl group, aZ-hydroxyethyl group. a

3'hydroxypropyl group, a Z-carboxyethyl group. a

or a chlorine atom at the 5-position; Z forms a benzol5 selenazole ringwhich is unsubstituted or substituted with a methyl group, an ethylgroup, a methoxy group, a phenyl group or a chloride atom at the5-position; R, and R each is a sulfosubstituted alkyl group, acarboxy-substituted alkyl group or a hydroxyalkyl group; and A is amethyl group.

3. The silver halide photographic emulsion as described in claim 1,wherein at least one of R, and R is a sulfosubstituted alkyl group andat least one of R and R, is a sulfosubstituted alkyl group.

4. The silver halide photographic emulsion as described in claim 1,wherein in the general formula (II) Z and 2, form benzimidazole ringssubstituted with chlorine atoms or fluorine atoms at the 5, 6, 5 and 6positions.

5. The silver halide photographic emulsion as described in claim 1,wherein R,, R R and R, are sulfosubstituted alkyl groups.

6. A color light sensitive material comprising a support having thereonthe silver halide photographic emulsion as described in claim I.

7. The silver halide photographic emulsion as described in claim 1,wherein said alkyl group for R, R, is an unsubstituted alkyl group, ahydroxyalkyl group, a carboxy-substituted alkyl group, asulfo-substituted alkyl group, an acetoxyalkyl group, a cyanoalkylgroup, a carbamoylalkyl group, a morpholinocarbonyl group, an allylgroup or a morpholinosulfonylalkyl group.

8. The silver halide photographic emulsion as described in claim 1,wherein Z, is a benzothiazole, 5- chlorobenzothiazole,S-bromobenzothiazole, 5- fluorobenzothiazole, SI-methylbenzothiazole,51- methoxybenzothiazole, S-methylcarbonylbenzothiazole,S-methoxycarbonylbenzothiazole, S-carboxybenzothiazole,S-hydroxybenzothiazole, 5- trifluoromethylbenzothiazole,5-cyanobenzothiazole, 5,-dimethylbenzothiazole,5,6-dimethoxybenzothiazole, 5,6-dichlorobenzothiazole,,B-naphthothiazole, benzoselenazole, 5-chlorobenzoselenazole, 5-bromoselenazole, 5-methylbenzoselenazole, 51- methoxybenzoselenazole or,B-naphthoselenazole ring; wherein Z is a benzoselenazole, 5-chlorobenzoselenazole, S-bromobenzoselenazole, 5- methylbenzoselenazoleor S-methoxybenzoselenazole ring; wherein Z, and Z, each is al-methyl-S- chlorobenzimidazole, l-methyl-5-fluorobenzimidazole,

l-methyl5 ,o-dichlorobenzimidazole, l-ethyl-5- chlorobenzimidazole,l-ethyl-5-fluorobenzimidazole, l-methyl-S ,6-dichlorobenzimidazole,l-ethyl-5 ,6- difluorobenzimidazole, l-propyl-S- chlorobenzimidazole,l-propyl-5-fluorobenzimidazole, l-propyl-5 ,-dichlorobenzimidazole,l-propyl-5 ,6- difluorobenzimidazole, l-allyl-5-chlorobenzimidazole,

3carboxypropyl group, a 4-carboxybutyl group, a 2- sulfoethyl group, a3-sulfopropyl group, a 3-sulfobutyl group, a 2-[3-sulfopropoxy1ethylgroup, a 2-hydroxy3- sulfopropyl group, a 3-sulfopropoxyethoxyethylgroup, an acetoxyethyl group, a cyanopropyl group, a fi-carbamoylethylgroup, a ,8-(4-morpholinocarbonyl)ethyl group, or a6-(4-morpholinosulfonyl)butyl group.

9. The silver halide photographic emulsion as described in claim 1,including a cyan coupler.

10. The silver halide photographic emulsion as described in claim 1,wherein the supersensitizing com bination containsanhydro-5,5,9-trimethyl-3,3-di(3- sulfopropyl)selenacarbocyaninehydroxide and anhydro-5,5 ,6,6-tetrachlorol ,1 -diethyl-3 ,3 'di( 3-sulfopropoxyethoxyethyl)benzimidazolocarbocyanine hydroxide mono sodiumsalt.

11. The silver halide photographic emulsion as described in claim 1,wherein the supersensitizing combination containsanhydro-5,5,9-trimethyl-3,3-di(3- sulfopropyl)selenacarbocyaninehydroxide and anhydro-5,5 ,6,6-tetrachlorol ,l ,3-triethyl-3 3-sulfopropyl)benzimidazolocarbocyanine hydroxide.

12. The silver halide photographic emulsion as described in claim 1,wherein the supersensitizing combination containsanhydro-S,5,9-trimethyl3,3"di(3- sulfopropyl)sclenacarbocyaninehydroxide and anhydro-3-(2-carbamoylethyl )-5,5',6,6'-tetrachloro l ldiethyl-3'-sulfopropyl benzimidazolocarbocyaninc hydroxide.

13. A silver halide photographic emulsion containing a supersensitizingcombination of at least one sensitizing dye represented by the followinggeneral formula wherein Z, represents the atoms necessary to form abenzothiazole ring, a benzoselenazole ring, a ,B-naphthothiazole ring ora B-naphthoselenazole ring; Z represents the atoms necessary to form abenzoselenazole ring; A represents a hydrogen atom or an alkyl group; R,and R each represents an alkyl group, at least one of R, and R being ahydroxyalkyl group; a carboxysubstituted alkyl group or asulfo-substituted alkyl group; X represents an acid anion group; and mrepresents l or 2 and, when the dye forms an intramolecular salt, Inrepresents 1; and at least one sensitizing dye represented by thegeneral formula (ll)

1. A SILVER HALIDE PHOTOGRAPHIC EMULSION CONTAINING A SUPER SENSITIZINGCOMBINATION OF AT LEAST ONE SENSITIZING DYE REPRESENTED BY THE FOLLOWINGGENERAL FORMULA (1)
 2. The silver halide photographic emulsion asdescribed in claim 1, wherein in the general formula (I) Z1 forms a Beta-naphthothiazole ring, a Beta -naphthoselenazoLe ring or a benzothiazoleor benzoselenazole ring which is unsubstituted or substituted with amethyl group, an ethyl group, a methoxy group, a phenyl group or achlorine atom at the 5-position; Z2 forms a benzoselenazole ring whichis unsubstituted or substituted with a methyl group, an ethyl group, amethoxy group, a phenyl group or a chloride atom at the 5-position; R1and R2 each is a sulfosubstituted alkyl group, a carboxy-substitutedalkyl group or a hydroxyalkyl group; and A is a methyl group.
 3. Thesilver halide photographic emulsion as described in claim 1, wherein atleast one of R1 and R2 is a sulfosubstituted alkyl group and at leastone of R3 and R4 is a sulfosubstituted alkyl group.
 4. The silver halidephotographic emulsion as described in claim 1, wherein in the generalformula (II) Z3 and z4 form benzimidazole rings substituted withchlorine atoms or fluorine atoms at the 5, 6, 5'' and 6'' positions. 5.The silver halide photographic emulsion as described in claim 1, whereinR1, R2, R3 and R4 are sulfo-substituted alkyl groups.
 6. A color lightsensitive material comprising a support having thereon the silver halidephotographic emulsion as described in claim
 1. 7. The silver halidephotographic emulsion as described in claim 1, wherein said alkyl groupfor R1 - R4 is an unsubstituted alkyl group, a hydroxyalkyl group, acarboxy-substituted alkyl group, a sulfo-substituted alkyl group, anacetoxyalkyl group, a cyanoalkyl group, a carbamoylalkyl group, amorpholinocarbonyl group, an allyl group or a morpholinosulfonylalkylgroup.
 8. The silver halide photographic emulsion as described in claim1, wherein Z1 is a benzothiazole, 5-chlorobenzothiazole,5-bromobenzothiazole, 5-fluorobenzothiazole, 51-methylbenzothiazole,51-methoxybenzothiazole, 5-methylcarbonylbenzothiazole,5-methoxycarbonylbenzothiazole, 5-carboxybenzothiazole,5-hydroxybenzothiazole, 5-trifluoromethylbenzothiazole,5-cyanobenzothiazole, 5,6-dimethylbenzothiazole,5,6-dimethoxybenzothiazole, 5,6-dichlorobenzothiazole, Beta-naphthothiazole, benzoselenazole, 5-chlorobenzoselenazole,5-bromoselenazole, 5-methylbenzoselenazole, 51-methoxybenzoselenazole orBeta -naphthoselenazole ring; wherein Z2 is a benzoselenazole,5-chlorobenzoselenazole, 5-bromobenzoselenazole, 5-methylbenzoselenazoleor 5-methoxybenzoselenazole ring; wherein Z3 and Z4 each is a1-methyl-5-chlorobenzimidazole, 1-methyl-5-fluorobenzimidazole,1-methyl-5,6-dichlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole,1-ethyl-5-fluorobenzimidazole, 1-methyl-5, 6-dichlorobenzimidazole,1-ethyl-5,6-difluorobenzimidazole, 1-propyl-5-chlorobenzimidazole,1-propyl-5-fluorobenzimidazole, 1-propyl-5,6-dichlorobenzimidazole,1-propyl-5,6-difluorobenzimidazole, 1-allyl-5-chlorobenzimidazole,1-allyl-5-fluorobenzimidazole, 1-allyl-5,6-dichlorobenzimidazole,1-allyl-5,6-difluorobenzimidazole, 1-phenyl-51-chlorobenzimidazole,1-phenyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole,1-phenyl-5,6-difluorobenzimidazole ring; wherein said alkyl group for Ais a methyl group, an ethyl group, or a propyl group; wherein said R1 toR4 each is a methyl group, an ethyl group, a propyl group, a2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-carboxyethyl group, a3-carboxypropyl group, a 4-carboxybutyl group, a 2-sulfoethyl group, a3-sulfopropyl group, a 3-sulfobutyl group, a 2-(3-sulfopropoxy)ethylgroUp, a 2-hydroxy-3-sulfopropyl group, a 3-sulfopropoxyethoxyethylgroup, an acetoxyethyl group, a cyanopropyl group, a Beta-carbamoylethyl group, a Beta -(4-morpholinocarbonyl)ethyl group, or adelta -(4-morpholinosulfonyl)butyl group.
 9. The silver halidephotographic emulsion as described in claim 1, including a cyan coupler.10. The silver halide photographic emulsion as described in claim 1,wherein the supersensitizing combination containsanhydro-5,5'',9-trimethyl-3,3''-di(3-sulfopropyl)selenacarbocyaninehydroxide and anhydro-5,5'',6,6''-tetrachloro-1,1''-diethyl-3,3''-di(3-sulfopropoxyethoxyethyl)benzimidazolocarbocyanine hydroxide mono sodiumsalt.
 11. The silver halide photographic emulsion as described in claim1, wherein the supersensitizing combination containsanhydro-5,5'',9-trimethyl-3,3''-di(3-sulfopropyl)selenacarbocyaninehydroxide and anhydro-5,5'',6,6''-tetrachloro-1,1'',3-triethyl-3''-(3-sulfopropyl)benzimidazolocarbocyanine hydroxide.
 12. The silver halidephotographic emulsion as described in claim 1, wherein thesupersensitizing combination containsanhydro-5,5'',9-trimethyl-3,3''-di(3-sulfopropyl)selenacarbocyaninehydroxide andanhydro-3-(2-carbamoylethyl)-5,5'',6,6''-tetrachloro1,1''-diethyl-3''-sulfopropyl benzimidazolocarbocyanine hydroxide.
 13. A silver halidephotographic emulsion containing a supersensitizing combination of atleast one sensitizing dye represented by the following general formula(I)